Process for breaking petroleum emulsions



Patented Feb. 20, 1951 UNITED STATES PATENT OFFICE PROCESS FOR BREAKINGPEfIROLEUM EMULSIONS Melvin DeGroote, St; Louis, and BernhardkeiserpWebster Groves, Mo., assignors to Petrolit e, Corporation, LtdWilmington,'l)el .,]a corpora;-

tion of Delaware No Drawing. Application December 10, 1948,

Serial No. 64,454.,

19 Claims. 1

This invention relates to 1 processes or pro:

cedures particularly adapted for prev ntin breaking, or resolvingemulsionspf the water-in; oil type, and particularly petroleumemulsions.- This invention is a continuation-in-part ofour co.-pendingapplication, Serial No, 726,2 1 2, fi1ed February 3, "1947 (nowabandoned). See also our co-pending application, Serial No. 8,731, filedFebruary 16, 1948 (now, abandoned) and also,

Serial No. 42,134, filed August 2, 1948 (nowaban doned). Attention isdirected also to our co}- pending application, Serial No. 64 ,169, fi1ed December 10, 1948.

Complementary to the above aspect oftl'ie i ne,

vention is our companion invention concerned with thenew chemicalproducts or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of suchchemical compounds, -pro d-. ucts, and'the like, in various otherartsand in-. dustries, along with the method for 'manufaca etc., andwhich comprise fine droplets of naturally-occurring waters or brinesdispersed in a more or less permanent state throughout the oil whichconstitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been. prepared under controlled conditions frommine. eral oil, such as crude oil and relatively soft waters or weakbrines. Controlled emulsificas tion and subsequent demulsification underthe conditions just mentioned are ofsignificant value.

in removing impurities, particularly inorganic salts, from pipeline oil.

Demulsification asv contemplated in .the present application includes,the preventive step of com,- mingling the demulsifier with the aqueouscomponent which would or might subsequently be come either phase of theemulsion in the absence of such precautionary measure. Similarly, such01 (A) an alpha-beta alkylene oxide having not 2. demulsifier may bemixed with the hydrocarbon component.

Briefly stated, the present process is concerned with the breaking orresolving of petroleum emulsions by means of certain esters which are,in turn, derivatives of specific synthetic products. These products;are, in turn the 'oxyalkylated derivatives of certain resins hereinafterspecified.

Thus, the present, process is. concerned. with breaking petroleumemulsions of the water-in-oil type characterized by subjecting theemulsion to the action of a demulsifier including a hydrophile ester inwhich the acyl radical is that of a detergent-forming monocarboxy acidhaving at least 8 and not over 32 carbon atoms, and the alcoholicradical isth'at of certain hydrophile polyhydric synthetic productsjsaid; hydrophile synthetic products. being oxyalkylation products morethan 4 carbon atoms and selected from the class consisting of ethyleneoxide, propylene oxide, butylene oxide, glycide and methylglycide, and(B) an oxyalkylation-susceptible, fusible, organic solvent-soluble,water-insoluble phenolaldehyde" resin; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms,

and reactive toward said phenol; said resin being formed in thesubstantial absence of trifunc tionalphenols; said phenol being of theformula icals, and hydroxybutylene radicals, and n is a numeral varyingfrom 1 to 20; with the proviso that at least 2 moles of alkylene oxidebe introduced for each phenolic nucleus; and with the final proviso thatthe hydrophile properties of said ester, as well as said oxyalkylatedresin, in an equal weight of xylene are sufficient to produce anemulsion when said xylene solution is shaken vigorously with one tothree volumes of water. I

For purpose of convenience what is said hereinafter will be divided intofour parts. Part 1 will be concerned with the production of the resinfrom a difunctional phenol and an aldehyde; Part 2 will be concernedwith the oxyalkylation of the resin so as to convert it into ahydrophile hydroxylated derivative; Part 3 will be concerned with theconversion of the immediately aforementioned derivative into a total orpartial ester by reaction with an acid, an ester, or other functionalderivative, so as to obtain a compound of the kind previously specifiedand subsequently described in detail; and Part 4 will be concerned withthe use of such esters as demulsifiers as hereinafter described.

PART 1 As to the preparation of the phenol-aldehyde resins reference ismade to our co-pending applications, Serial Nos. 8,730 and 8,731, bothfiled February 16, 1948 (both now abandoned). In such co-pendingapplications we described a fusible, organic solvent-soluble,water-insoluble resin polymer of the formula In such idealizedrepresentation 71 is a numeral varying from 1 to 13 or even more,provided that the resin is fusible and organic solvent-soluble. R is ahydrocarbon radical having at least 4 and not over 8 carbon atoms. Inthe instant application B may have as many as 12 carbon atoms, as in thecase of a resin obtained from a dodecylphenol. In the instant inventionit may be first suitable to describe the alkylene oxides employed asreactants, then the aldehydes, and finally the phenols, for the reasonthat the latter require a more elaborate description.

The alkylene oxides which may be used are the alpha-beta oxides havingnot more than 4 carbon atoms, to wit, ethylene oXide, alpha-betapropylene oxide, alpha-beta butylene oxide, glycide, and methylglycide.

Any aldehyde capable of formin a methylol or a substituted methylolgroup and having not more than 8 carbon atoms is satisfactory, so longas it does not possess some other functional group or structure whichwill conflict with the resinification reaction or with the subsequentoxyalkylation of the resin, but the use of formaldehyde, in its cheapestform of an aqueous solution, for the production of the resins isparticularly advantageous. Solid polymers of formaldehyde are moreexpensive and higher aldehydes are both less reactive, and are moreexpensive. Furthermore, the higher aldehydes may undergo other reactionswhich are not desirable, thus introducing dificulties into theresinification step. Thus acetaldehyde, for example, may undergo analdol condensation, and it and most of the higher aldehydes enter intoself-resinification when treated with stron acids or alkalies. On theother hand, higher aldehydes frequently beneficially affect thesolubility and fusibility of a resin. Thi is illustrated, for example,by the different characteristics of the resin prepared frompara-t-ei'flary amylphenol and formaldehyde on one handg' and acomparable product prepared from the same phenolic reactant andheptaldehyde on the other hand. The former, as shown in certainsubsequent examples, is a hard, brittle, solid, whereas the latter issoft and tacky, and obviously easier to handle in the subsequentoxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. Theemployment of furfural requires careful control for the reason that inaddition to its aldehydic function, furfural can form vinylcondensations by virtue of its unsaturated structure. The production ofresins'from furfural for use in preparing reactants for the presentprocess is most conveniently conducted with weak alkaline catalysts andoften with alkali metal carbonates. Useful aldehydes, in addition toformaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde,Z-ethylhexanol, ethyl-butyraldehyde, heptaldehyde, and benzaldehyde,furfural and glyoxal. It would appear that the use of glyoxal' should beavoided due to the fact that it is tetrafunctional. However, ourexperience has been that, in resin manufacture and particularly asdescribed herein, apparently only one of the aldehydic functions entersinto the resinification reaction. The inability of the other aldehydicfunction to enter into the reaction is presumably due to sterichindrance. Needless to say, one can use a mixture of two or morealdehydes although I usually this has no advantage.

Resins of the kind which are used as intermediates in this invention areobtained with the use of acid catalysts or alkaline catalysts, orwithout the use of any catalyst at all. Among the useful alkalinecatalysts are ammonia, amines, and quaternary ammonium bases. It isgenerally accepted that when ammonia and amines are employed ascatalysts they enter into the condensation reaction and, in fact, mayoperate by initial combination with the aldehydic reactant. The compoundhexamethylenetetramine illustrates such a combination. In light of thesevarious reactions it becomes difficult to present any formula whichwould depict the structure of the various resins prior to oxyalkylation.More will be said subsequently as to the difference between the use ofan alkaline catalyst and an acid catalyst; even in the use of analkaline catalyst there is considerable evidence to indicate that theproducts are not identical where different basic materials are employed.The basic materials emnols, such as substituted naphthols. Specifically,

monocyclic is limited to the nucleus in which the hydroxyl radical isattached. Broadly speaking, where a 'substituent is cyclic, particularlyaryl, obviously in the usual sense such phenol is actually polycyclicalthough the phenolic hydroxyl is not attached to a fused polycyclicnucleus. Stated another way, phenols in which the hydroxyl groupisdirectly attached to a condensed or fused polycyclic structure, areexcluded. This matter, however, is clarified by the followingconsideration. The phenols herein contemplated for reaction may beindicated by the following formula:

in which R is selected from the class consisting; of hydrogen atoms andhydrocarbon radicals having at least 4 carbon atoms and not more than 12carbon atoms, with the proviso that one occurrence of R is thehydrocarbon substituent and the other two occurrences are hydrogenatoms, and with the further provision that one or both of the 3 and 5positions may be methyl substituted.

The above formula possibly can be restated more conveniently in thefollowing manner, to wit, that the phenol employed is of the followingformula, with the proviso that R is a hydrocarbon substituent located inthe 2,4,6 position, again with the provision as to 3 or 3,5 methylsubstitution. This is conventional nomenclature, numbering the variouspositions in the usual clockwise manner, beginning with the hydroxylposition as one:

insare usually manufactured for the varnish trade and" oil solubilityis'of prime importance." Forthis reason, the common'reactants employedare butylated phenols, amylated phenols, phenyl phenols, etc. Themethods employed in manufacturing such resins are similar to thoseemployed in the manufacture of ordinary phenolformaldehyde resins, inthat either an acid or alkaline catalyst is usually employed. Theprocedure usually differs from that employed in the manufacture ofordinar phenol-aldehyde resins in that phenol, being water-soluble,reacts readily with an aqueous aldehyde solution without furtherdifficulty, while when a water-insoluble pheno] is employed somemodification is usually adopted to increase the interfacial surface andthus cause reaction to take place. A common solvent is sometimesemployed. Another procedure employs rather severe agitation to create alarge interfacial area. Once the reaction starts to a moderate degree,it is possible that both reactants are somewhat soluble in the partiallyreacted mass and assist in hastening the reaction. We have found itdesirable to employ a small proportion of an organic sulfa-acid as acatalyst, either alone or along with a mineral. acid like sulfuric orhydrochloric acid. For example, alkylated aromatic sulfonic acids areeffectively employed. Since commercial forms of such acids are commonlytheir alkali salts, it is sometimes convenient to use a small quantityof such alkali salt plus a small quantity of strong mineral acid, asshown in the examples below. If desired, such organic sulfo-acids may beprepared in situ in the phenol employed, by reacting concentratedsulfuric acid with a small proportion of the phenol. In such cases wherexylene is used as a solvent and concentrated sulfuric acid isemployed,'some sulfonation of the Xylene probably occurs to "produce thesulfo-acid. Addition of a solvent such as xylene is advantageous ashereinafter clescribed in detail. Another Variation of procedure is toemploy such organic sulfo-acids, in the form of their salts, inconnection'with an alkali-catalyzed resinification procedure. Detailedexamples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusibletype of resin by the acid catalytic procedure is that, since adifunctional phenol is employed, an excess of an aldehyde, for instanceformaldehyde, may be employedwithout too marked a change in conditionsof reaction and ultimate product. There is usually little, if

any, advantage, however, in usin an excess over and above thestoichiometric proportions for the reason that such excess may be lostand wasted. For all practical purposes the molar ratio of formaldehydeto phenol may be limited to 6.9 to 1.2., with 1.05 as the preferredratio, or sufiicicnt; at least theoretically, to convert the remainingreactive hydrogen atom of each terminal phenolic nucleus. Sometimes whenhigher aldehydes are used an excess of aldehydic reactant can bedistilled off and thus recovered from the reaction mass. This sameprocedure may be used with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularlyformaldehyde, may be increased over the simple stoichiometric ratio ofone-to-one or thereabouts. With the use of alkaline catalyst it has beenrecognized that considerably increased amounts of formaldehyde may beused, as much as two moles of formaldehyde, for example, per mole ofphenol, or even more, with the result that only a small-partof such al.-

b dehyde remainsquncombined oris subsequently liberated duringresinification. Structures which have been advanced to explain suchincreased use;

of aldehydes arethe following:

Sometimes conventional resinificaQtionproce dure is employed usingeither acid or alkaline catalysts to produce low-stage resins. Suchresins may be employed as such, or may be altered or converted intohigh-stage resins, or in any event, into resins of higher molecularweight, by heating along with the employment of vacuum so as to splitoff water or formaldehyde, or both. Generally speaking, temperaturesemployed, particularly with vacuum, may be in the neighborhood of 175 to250 C., or thereabouts.

It may be well to point. out,.however,,that the amount of formaldehydeused may and does usu ally aifect the length of the resin chain..Increasin the amount of the aldehydepsuchas formaldehyde, usuallyincreases the size of molecular weight of the polymer.

In the hereto appended claims there isgspecified, among other things,the resin polymer containing at least -3-phenolic nuclei.- SuchJminimummolecular size is most conveniently determined as a rule by cryoscopicmethodusing ben.-. zene, or some other suitable solvent, for instance,-one of those mentioned elsewhere herein as a,

solvent for such resins. As a matterof fact, using the procedures hereindescribed or any conven-. tional resinification procedure williyieldproducts,

usually having definitely in excess of 3 nuclei. In other words, a resinhaving an average of 4, or 5 /2 nuclei per unit is apt to be formed as aminimum in resinification, except under certain spe--.

cial conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures,substituting cymene, tetralin, etc., or some other suitable solventwhichboils or refluxes at a higher temperature, instead of xylene, insubsequent examples, and if, one doubles or triples the amount ofcatalyst, doubles or triples the time of refluxing, uses a marked excessof formaldehyde or other aldehyde, then the average size of the resin isapt to be distinctly.

Sometimes the expression The molecular ,weight, determinations, ofcourse, requirethat the product be completely toemployis that of Menziesand Wright (see J..

Am. jChem5Socfi43, 2309 and 2314 (1921)). Any suitable method fordetermining molecular weights will serve, although almost any procedureadopted has inherent limitations. A good'method for determining themolecular weights of resins, especially solvent-soluble resins, is thecryoscopic procedure of Krumbhaar which employs 'diphenylam'ine asa'solvent' (se'e"Coating andInk Resins, page 157, Reinhold PublishingSubsequent examples will illustrate the use of an acid catalyst, analkaline catalyst, and no catalyst. As far as resin manufacture per seis concerned, we prefer to use an acid catalyst, and particularly amixture of an organic sulfo-acid and a mineral acid, along with asuitable solvent,

distillation and heating. Although such procedure sometimes removes onlya modest amount or even perhaps no low polymer, yet it is almost certainto produce further polymerization. For

instance, acid catalyzed resins obtained in the usual manner and havinga molecular weight indicating the presence of "approximately 4 phe--nolic units or thereabouts may be subjected to such treatment, with theresult that one obtains a resin having approximately double thismolecular weight. g The. usual procedure is to use-asecondary step,heating the resin in the presence or absence of an inert gas, includingsteam,.or by use of- =vacuum. 1.

We have found that under the usual conditions? of resinificationemploying phenols of the kind here described, there is little or notendency to form binuclear compounds, i. e., dimers, resulting from thecombination, for example, of 2 moles of a phenol and one mole offormaldehyde, particularly where the substituent has 4 or 5 carbonatoms. Where the number of carbon atoms in a substituent approximatesthe upper limit specified herein, there may be some tendency todimerization. The usual procedure to obtain a dimer involves'anenormously large excess of the phenol, for instance, 8 to 10 moles permole of aldehyde. Substituted dihydroxydiphenylmethanes obtained fromsubstituted phenols are not resins as that term is used herein.

Although any conventional procedure ordinarily employed may be used inthe manufacture of the herein contemplated resins or, for that matter,such resins may be purchased in the open market, we have found itparticularly desirable .aetea to use the procedures described elsewhereherein, and employing a combination of an organic sulfo-acid and amineral acid as a catalyst, and xylene as a solvent. By way ofillustration, certainsubsequent examples are included, but it is to beunderstood the herein described invention is not concerned with theresins per 'se or with any particular method of manufacture but isconcerned with the use of reactants obtained by the subsequentoxyalkylation thereof. The phenol-aldehyde resins may be prepared in anysuitable manner.

Oxyalkylation, particularly oxyethylation which is the preferredreaction, depends on contact between a non-gaseous phase and a gaseousphase. It can, for example, be carried 'out by melting the thermoplasticresin and subjecting it to. treatment with ethylene oxide or the like,or by treating a suitable solution or suspension. Since the meltingpoints of the resins are often higher than desired in the initial stageof oxyethylation, we have found it advantageous to use a solution orsuspension of thermoplastic resin in an inert solvent such as xylene.Under such circumstances, the resin obtained in the usual manner isdissolved by heating in xylene under a reflux condenser or in any othersuitable manner.

.Sincexylene or an equivalent inert solvent is present or may be presentduring oxyalkylation,

it is obvious there is no objection to having a chlorine atom in thecompound may slowly combine with the alkaline catalyst employed inoxyethylation. Suitabl solvents may be selected from this group formolecular weight determinations.

The use of such solvents is a convenient expedient in the manufacture ofthe thermoplastic resins, particularly since the solvent gives a moreliquid reaction mass and thus prevents overheating, and also because thesolvent can be employed in connection with a reflux condenser and awater trap to assist in the removal of water of reaction and also waterpresent as part of the formaldehyde reactant when an aqueous solution offormaldehyde is used. Such aqueous solution, of course, with theordinary product of commerce containing about 37 to 40% formaldehyde, isthe preferred reactant. When such solvent is used it is advantageouslyadded at the beginning of the resinification procedure or before thereaction has proceeded veryfar.

The solvent can be removed afterwards by distillation with or Withoutthe use of vacuum, and

a final higher temperature can be employed to complete reaction ifdesired. In many instances it is mostdesirable to-permit part of thesolvent, particularly when it is inexpensive, e. g., xylene, to remainbehind in a predetermined amount so as to have a resin which can behandled more conveniently in the oxyalkylation stage. If a ,oxyalkylatedderivative.

dure. bus that trifunctional phenols aretolerable only room expensivesolvent, such. as decalin, is emthe neighborhood of T 5 of 1%, or evenless. The

amount of the usual trifunctional phenol, such as. hydroxybenzene ormetacresol, which can be tolerated is determined by the fact that actualcross-linking, if it takes place even infrequently, must not besufficient to cause insolubility at the 'completionof the resinificationstage or the lack of hydrophile properties at the completion of theoxyalkylation stage.

The exclusion of such trifunctional phenols as hydroxybenzene or.metacresol is not based on the fact that the mere random or occasionalinclusion of an unsubstituted phenyl nucleus in the resin molecule or inone of several molecules, for example, markedly alters thecharacteristics of the The presence of a phenyl radical having areactivehydrogen atom available or having a hydroxymethylol or a substitutedhydroxymethylol group present is a potential source of cross-linkingeither during resinification or oxyalkylation. Cross-linking leadseither to insoluble resins or to non-hydrophilic products resulting fromthe oxyalkylation proce- With this rationale understood, it is obviin aminor proportion and should not be, present to the extent thatinsolubility is produced in the resins, or.that the product resultingfrom, oxyalkylation is gelatinous, rubbery, or at least not hydrophile.As to the rationale of resinification, note particularly What is saidhereafter in differentiating between resoles, Novolaks, and resinsobtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organicsolvent-soluble resins are usually I linear but may be cyclic. Such morecomplicated structure may be formed, particularly if a .resin preparedin theusual manner is converted into a higherstage resin by heat treatment in vacuum as previously mentioned. This again is a reason foravoiding any opportunity for cross-linking due to. the presence ofanyappreciable amount of .trifunctional .phenol. In other words, thepresence of such reactant may cause. cross-linking in a conventionalresinification procedure, or in the oxyalkylation procedure, or in theheat and vacuum treatment if it is employed as part of resinmanufacture.

Our routine procedure in examining a phenol for suitability forpreparing intermediates to .be

used in practicing the invention is to prepare a a resin employingformaldehyde in excess (1.2 moles of formaldehyde per mole of phenol)and using an acid catalyst in the manner described in Example 1a of ourPatent 2,499,370 granted March "7, 1950. If the resin so obtained issolvent-solcially if the pro ortion is small. involving difunctionalnhenols only may also pro- "spit-595 11 hours. If the product soobtained is solvent-soluble and self-dispersing or emulsiflable, or hasemulsifying properties, the phenol is perfectly satisfactory from thestandpointof. trifunctional phenol content. The solvent may be removedprior to the dispersibility or emulsifiability test. When aproductbecomes rubbery .during' oxyalkylation due to'the presence 'of asmall amount of trireactive phenol, as previously mentioned, or for someother reason, it may become extremely insoluble. and no longer qualifiesas being hydrophile as herein specified. Increasing the size of thealdehvdic nuc eus, for instance using heptaldehyde ins ead offormaldehyde, increases tolerance for trifunctional phenol. The presenceof a trifunctional or tetrafunctional phenol (such as resorcinol orbisph'enol A) is apt to'produce detectable cross-linking andinsolubilization but will not necessarily do so, espe- Resinificationduce insolubilization. although this seems to be an anomaly or acontradiction of what is sometimes said, in regard to resinificationreactions involving difunctional phenols only. This is. presumably dueto cross-linking. This appears to-be contradictory to ,what onemightexpectin light of the theory of functionality in resinification. Itis true that under ordinary circumstances. or rather under thecircumstances of conventional resin manufacture, the procedures.employing' difunctional phenols are very apt to, and almost invariablydo, yield solvent-soluble, fusible resins. However, when conventionalprocedures are emploved in connection with resins for varnishmanufacture or the like, there is involved the matter of color,solubility in oil. etc. When resins of the same. type are manufacturedfor the herein contemplatedpurpose. i. e., as a raw material to besubjected to oxyalkylation, 'suchcriteria. of selection are no longerpertin nt. Stated another way. one may use more drastic conditionsofresinification than thoseordina'rily employed to produce resins forthe present purposes. Such more drastic conditions of resinification mayinclude increased amounts of catalyst, higher temperatures, longer timeof reaction, subsequent reaction involving heat alone or in combinationwith vacuum, etc. cerned with the resinification reactions which yieldthe bulk of ordinar resins from difunctional phenols but also andparticularly with the minor reactions of ordinary resin manufacturewhich are of importance in the present invention for the reason thatthey occur under more drastic conditions of resinification which may beemployed advantageously at times, and they may lead to cross-linking.

There ore. one is not only con- In this connection it may be well topoint out that part of these reactions are now understood or explainableto a greater or lesser degree in light of a most recent investigation,Reference is made to the researches of 'Zinke and his coworkers,Hultzsch and his associates, and to von Eulen and his co-workers, andothers. As to a bibliography of such investigations, see Carswell,Phenoplasts, chapter 2. These investigators limited muchof their work toreactions involving phenols havin two or .less reactive hydrogen atoms.Much of what appears in these most recent and most up-to-dateinvestigations is pertinent to the present invention insofar that muchof it is referring to resinification involving difunctional phenols.

a. most typical typefof fusible resin and forget for the time that suchresin, at least under certain circumstances, is susceptible to furthercomplications. Subsequently in the text it will be pointed out thatcross-linking or reaction with excess formaldehyde may take place evenwith one of such most typical type resins. This point is made for thereason that insolubles must be avoided in order to obtain the productsherein contemplated for use as reactants.

The typical type of fusible resin obtained from a para-blocked orortho-blocked phenol is clearly differentiated from the Novolak type orresole type of resin. Unlike the resole type, such ftypic'al typepara-blocked or ortho-blocked phenol resin may be heated indefinitelywithout passing into an infusible stage, and in this respect is similarto a Novolak. Unlike the Novolak type the addition of a furtherreactant, for instance, more aldehyde, does not ordinarily alter,fusibility of the difunctional phenol-aldehyde of formaldehyde to oneof phenol, along with an alkaline catalyst. This peculiar hardening orcuring or cross-linking of resins obtained from difunctional' phenolshas been recognized by various authorities. The intermediates hereinused must be hydrophile or sub-surface-active or surfaceactive ashereinafter described, and this preeludes the formation of insolublesduring resin manufacture or the subsequent stage of resin manufacturewhere heat alone, or heat and vacuum, are employed, or in theoxyalkylation procedure. In its simplest presentation the rationale ofresinification involving formaldehyde,'for example, and a difunctionalphenol would not be expected to form cross-links. However, cross-linkingsometimes occurs and it may reach the objectionable stage. However,provided that the preparation of resins simply takes into cognizance thepresent knowledge of the subject, and employing preliminary, exploratoryroutine examinations as herein indicated, there is not the slightestdifficulty in preparing a very large number of resins of various typesand from various reactants, and by means of different catalysts bydifferent procedures, all of which are eminently suitable for the hereindescribed purpose.

Now returning to the thought that cross-linking can take place, evenwhen difunctional phenols are used exclusively, attention is directed toth following: Somewhere during the course of resin manufacture there maybe a potential cross-linking combination formed but actual cross-linkingmay not take place until the subsequent stage is reached, i. e., heatand vacuum stage, or oxyalkylation stage. This situation may be relatedor explained in terms of a theory of flaws, or Lockerstellen, which isemployed in explaining flaw-forming groups due to the fact that a CHzOHradical and H atom may not lie in the same plane in the manufacture ofordinary phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolubles may berelated to the aldehyde used and the ratio of aldehyde,particularlyformaldehyde, insofar that, a. slight variation may, under circumstancesnot understandable, produce insolubilization. The formation ofthemsoluble-resin is apparently very sensitive to the quantity offormaldehyde. employed and a. slight increase in the proportion offormaldehyde may lead to the formation of insoluble gellumps. j Thecause of insoluble resin formation is not clear, and nothing is known asto thestructure of these resins.

All that has been said previously hereinas regards resinification hasavoided ;the specific reference to activity ofa methylene hydrogen atom.Actually there is a possibility thatunder some, drasticconditions;cross-linking may take place through formaldehyde addition tothe methylene bridge, or some othenreactionjnvolving a methylenehydrogen atom.

Finally, there is some evidence that, although th meta positions are notordinarily reactive,

, possibly at times methylol groups or the like are formed at the metapositions; and if this were the case it may be a suitableexplanationof'abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instanceformaldehydeds not to be taken ,as a criterion; of rejection-foruse as areactant.

In other words a phenol-aldehyde resin which is thermoplastic andsolvent-soluble, particularly if xylene-soluble, is perfectly.satifactory even tively soft or pitchlike resin at ordinarytemperature. Such resins become comparatively fluid at 110 to 165"; C.as a rule and thus can be readily oxyalkylated, preferablyoxyethyl-ated, without the use of a solvent.

Reference has been made to the use of the word fusible. Ordinarily" athermoplastic resin is identified as onewhich canbe heatedrepeatedly andstill not lose its thermoplasticity. It is recognized, however, that onemay have a resin which; is initially: thermoplastic but on repeatedheating may become insoluble in an organic solvent, or at least nolonger thermoplastidzdue to the fact that certain changes take placevery slowly. As far. as the present inventionis concerned, it is obviousthat a resin to be suitable need only be sufficiently fusible topermitprocessing to produce our oxyalkylated products and not yieldinsolubles or cause insolubilization or gel formation, or rubberiness,as previously described. Thus resins which are, strictly speaking,fusible but not necessarily thermoplastic in the most rigid sense thatsuch terminology would be applied to the mechanical properties of aresin, are useful intermediates. The bulk of all fusible resins 0f thekind herein described are thermoplastic.

The fusible or thermoplastic resins, or solventsoluble resins, hereinemployedas reactants, are wa o ubl or veno apprec able. hyd oture.

v.phile properties. The hydrophile proper-tyis-introduced by-oxyalkylation. In the hereto apployed, particularly fordemulsification, it is obyious that the resins can be obtained by one ofa number of procedures. In the first place, suitableresins are marketedby a number of com- .panies and can be purchasedin the open market;:iHgthafiBfiDI 13 34 therearea w al h of examples of suitable resinsdescribed in the litera- The third procedure is to follow the directionsof the present application.

The polyhydric reactants, i. e., theoxyalkylation-susceptible,water-insoluble, organic solventsoluble,fusible, phenol-aldehyde resins derived from difunctional phenols, usedas intermediates to produc the products used in accordance with theinvention, are exemplified'by Examples Nos.

. lathrough 03a of our Patent 2,499,370, granted March '7, 1950, andreference is made to that patent for examples of the oxyalkylated resinsused as intermediates.

aPrevious reference has been made to the use of a single phenol asherein specified, or a single reactive aldehyde, or a singleoxyalkylating agent. Obviously, mixtures of reactants may be employed,as for example. a mixture of para-butylphenol and para-amylphenol, oramixture of para-butylphenol and para-hexvlphenol, or parabutylphenoland para-phenylphenol. It is extremely difficult to depict the structureof a resin derived from a single phenol. When mixtures of phenols areused, even in equimolar porportions,

the structure of the resin is even more indeter- -minable. In-otherwords, a mixture involving para-butylphenol and para-amylphenol mighthave an alternation of the two nuclei or one might have a series ofbutylated nuclei and then a series of amylated nuclei. If a mixture ofaldehydes is employed, for instance, acetaldehyde and butyraldehyde,oracetaldehyde and formaldehyde;

or benzaldehyde and acetaldehyde, the final structure of the resinbecomes even more complicated and possibly depends on the relativereactivity of the aldehydes. For that matter, one might be producingsimultaneously two; different resins, in what would actually beamechanical mixture, although such mixture might exhibit some uniqueproperties as compared with a mixture of the same two resins preparedseparately. Similarly, as has been suggested, onemight use acombinationof oxyalkylating agents; for instance, one might partially oxyalkylatewith ethylene oxide and then finish off with propylene oxide. It isunderstood that the oxyalkylated derivatives of such resins, derivedfrom such plurality of reactants, instead ofbeing limited to a singlereactant from each of the three classes, is

contemplated and here included for the reason that they are obviousvariants.

PART 2 -Having, obtained a suitable resin of the kind described, suchresin issubjecced to treatment a with a low molal reactive alpha-betaolefin oxide so as ,to render the product distinctly hydro phileinnature as, indicated by the fact that it becomes self-emulsifiable ormiscible or soluble .in;water, or selfdispersible or has emulsifyingepre t e i e ol fi ox de m lpyeda e c ar- '15 acterized by the fact thatthey contain not over 4 carbon atoms and are selected from the classconsisting of ethylene oxide, propylene oxide, bu-

tylene oxide, glycide, and methylglycide. Glycide and may be bestconsidered as derivatives of or substituted ethylene oxides. Thesolubilizin effect of the oxide is directly proportional to thepercentage of oxygen present, or specifically, to the oxygen-carbonratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is2:3; and in methyl glycide, 1:2. In such compounds, the ratio is veryfavorable to the production of hydrophile or surfaceactive properties.However, the ratio, in propylene oxide, is 1:3, and in butylene oxide,1:4. Obviously, such latter two reactants are satisfactorily employedonly where the resin composition is such as to make incorporation of thedesired property practical. In other cases, they may produce marginallysatisfactory derivatives, or even unsatisfactory derivatives. They areusable in conjunction with the three more favorable alkylene oxides inall cases. For instance, after one or several propylene oxide orbutylene oxide molecules have been attached to the resin molecule,oxyalkylation may be satisfactorily continued using the more favorablemembers of the class, to produce the desired hydrophile product. Usedalone, these two reagents may in some cases fail to produce sufficientlyhydrophile derivatives because of their relatively low oxygen-carbonratios.

Thus, ethylene oxide is much more effective than propylene oxide, andpropylene oxide is more effective than butylene oxide. I-Iydroxypropylene oxide (glycide) is more effective than propylene oxide.Similarly, hydroxy butylene oxide (methyl glycide) is more effectivethan butylene oxide. Since ethylene oxide is the cheapest alkylene oxideavailable and is reactive, its use is definitely advantageous, andespecially in light of its high oxygen content. Propylene oxide is lessreactive than ethylene oxide, and butylene oxide is definitely lessreactive than prop-ylene oxide. On the other hand, glycide may reactwith almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the initial reactantsused in the practice of the present invention are prepared isadvantageously catalyzed by the presence of an alkali. Useful alkalinecatalysts include soaps, sodium acetate, sodium hydroxide, sodiummethylate, caustic potash, etc. The amount of alkaline catalyst usuallyis between 0.2% to 2%. The temperature employed may vary from roomtemperature to as high as 200' C. The reaction may be conducted with orwithout pressure, i. e., from zero pressure to approximately 200 or even300 pounds gauge pressure (pounds per square inch). In a general way,the method employed is substantially the same procedure as used foroxyalkylation of other organic materials having reactive phenolicgroups.

It may be necessary to allow for the acidity of a resin in determiningthe amount of alkaline catalyst to be added in oxyalkylation. Forinstance, if a nonvolatile strong acid such as sulfuric acid is used tocatalyze the resinification reaction, presumably after being convertedinto a sulfonic acid, it may be necessary and is usually advantageous toadd an amount of alkali equal 'stoichiometrically "to such acidity, andinclude added alkali over and above this amount as the alkalinecatalyst.

It is advantageous to conduct the oxyethylation in presence of an inertsolvent such as xylene, cymene, decalin, ethylene glycol diethylether,diethyleneglycol diethylether, or the like, although with many resins,the oxyalkylatio-n proceeds sat 'isfactorily without a solvent.

Since xylene is cheap and may be permitted to be present in the finalproduct used as a demulsifier, it is our preference to use xylene. Thisis particularly true in the manufacturing of products from low-stage"resins, i. e., of 3 and up to and including '7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated,the pressure readings of course represent total pressure, that is, thecombined pressure due to xylene and also due to ethylene oxide orwhatever other oxyalkylating agent is used. Under such circumstances itmay be necessary at times to use substantial pressures to obtaineffective results, for instance, pressures up to 300 pounds along withcorrespondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such asxylene can be eliminated in either one of two ways: After theintroduction of approximately 2 or 3 moles of ethylene oxide, forexample, per phenolic nucleus, there is a definite drop in the hardnessand melting point of the resin. At this stage, if xylene or a similarsolvent has been added, it can be eliminated by distillation (vacuumdistillation if desired) and the subsequent intermediate, beingcomparatively soft and solvent-free, can be reacted further in the usualmanner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with suchsolvent present and then eliminate the solvent by distillation in thecustomary manner.

Another suitable procedure is to use propylene oxide or butylene oxideas a solvent as well as a reactant "in the earlier stages along withethylene oxide, for instance, by dissolving the powdered resin inpropylene oxide even though oXyalkylation is taking place to a greateror lesser degree. After a solution has been obtained which representsthe original resin dissolved in propylene oxide or butylene oxide, or amixture which includes the oxyalkylated product, ethylene oxide is addedto react with the liquid mass until hydrophile properties are obtained.Since ethylenepxide is more reactive than propylene oxide or butyleneoxide, the final product may contain some unreacted propylene oxide orbutylene oxide which can be eliminated by volatilization or distillationin any suitable manner.

Attention is directed to the fact that the resins herein described mustbe fusible or soluble in an organic solvent. Fusible resins invariablyare soluble in one or more organic solvents such as those mentionedelsewhere herein. It is to be emphasized, however, that the organicsolvent employed to indicate or assure that the resin meets thisrequirement need not be the one used in oxyalkylation. Indeed, solventswhich are susceptible to oxyalkylation are included in this group oforganic solvents. Examples of such solvents are alcohols andalcohol-ethers. However, where a resin is soluble in an organic solvent,there are usually available other organic solvents which are notsusceptible to oxyalkylation, useful for the oxyalkylation step. In anyevent, the

Organic solvent-soluble resin can be finely powdered, for instance to100 to 200 mesh, and a slurry or suspension prepared in xylene or thelike, and subjected to oxyalkylation. The fact that the resin is solublein an' organic solvent or the fact that it is fusible means that itconsists of separate molecules. Phenol-aldehyde resins of the typeherein specified possess reactive hydroxyl groups and are oxyalkylationsusceptible.

Considerable of what is said immediately hereinafter is concerned withability to vary the hydrophile properties of the hydroxylatedintermediate reactants from minimum hydrophile properties to maximum'hydrophile properties. Such properties in turn, of course, are effectedsubsequently by the acid employed for esterification and thequantitative nature of the esterification itself, i. e., Whether it istotal or partial. It may be well, however, to point out what has beensaid elsewhere in regard to the hydroxylated intermediate reactants.See, for example, our copending applications, Serial Nos. 8,730'and8,731, both .filed February 16, 19.48, and Serial No. 42,- 133, filedAugust 2, 1948, and Serial No. 42,134, filed August 2, 1948 (all fourcases'now abandonedl. The reason is that the esterification, dependingon the acid selected, may. vary the hydrophile-hydrophobe balance in onedirection or. the other, and also invariably causes the development ofsome property'whichmakes it inherently different from the two reactantsfrom which the derivative ester is obtained.-

Referring to the hydrophile hydroxylated intermediates, even moreremarkable and equally difficult to explain, are the, versatility. "andthe' utility of these compounds considered as chen1- ical reactants asone goes. from minimum' hydrophile property toultimate maximumhydrophile' property. -For instance, minimum hydro phile property "maybe described roughly; as. the point where twoethylenejoxy radicals ormodel: ately "in excess thereof are introduced per'phen olic'hydroxyl;Such minimum hydrophile property or sub"-'surface-'acitivity or] minimums'url face-activity means that "the product shows at" least emulsifyingproperties or self-dispersion in cold or even in'warm distilledw'ater"(15", 110 40: C. in concentrations of 0.5%*to, 5.0 Thesematerials are generally more soluble inycold waterQ than warm water, and-may'eyen be-very insolublei 50 in boiling water.- Moderately hightemperatures aid in reducing the viscosity'of: the solute under.examination: Sometimes' if one, i continues to shake "a'hot' solution,even though cloudy or; cone taining an insoluble phase-one finds. thatsolution 55 takes place to give a homogeneous, phase as the mixture"cools); Such: self d-ispersion tests are conducted in the absence of aninsoluble solvent."

Wheri the hydrophile-hydrophobe balance is above the indicated minimum'(2fm'oles of ethyleBO ene oxide per-phenolic nucleus or theequivalent Ibutiinsuficient to give a solas described irnm'ediat'ely preceding,then, and in thateventhydrophile"properties are indicatedby' the factthat one can produce an emulsion by having '0 present 10% to 50%Oran-inert solventsuch 'asf' xylene Allthat o e need to do is to have'axylenesolution within the range of 5(lto 90 parts, by weight ofoxyalkylated derivatives and 50'to 10 arts byweig'ht of xylene and mix fsuch some n 'withjo'ne, two or j three ftiiriesits' volume of 'dis -f'tilled water and shake vigprousl'y so' as to strain; an emulsion whichmay" be of the, oil in-wal telrf' typeor thewater-inoil l'iill(usuallythe former) surrace-a'ctiiity is not suitably determinedinthi's' Weprefer simply to use the xylene diluted deriva'tives, whichare described elsewhere, for this test rather than evaporate the solventand employ any more elaborate tests, if the solubility is not sufiicientto permit the simple sol test in water previously noted.

If the product is'not readily water soluble it may be dissolved in ethylor methyl alcohol, ethylene glycol diethylether, or diethylene glycoldiethylether, with a little acetone added if required, making a ratherconcentrated solution, for instance 40% to and then adding enou'gh'ofthe c'oncentrated alcoholic or equivalent solution to' give thepreviously suggested 0.5% to 5.0% strength solution. 'If-the productself-dispersmg (i. e., if the oxyalkylated product is a liquid oraliquid solution self-emulsifiable) such sol or dispersion'is referred toas at least semi-stable in the sense thatsols, emulsions, or dispersionsprepared are relatively stable, if they remain at least for some periodof 'time, for instance '30 minutes to two hours, before showing anymarked separation. Such tests are conducted at room ternperature (22C.)'. Needless'to say, a test can be made in presence of an insolublesolvent such as 5% to 15% of xylene, as notedin previous examples. Ifsuch mixture, i. e., containing alwaterinsoluble solvent, is at leastsemi-stable, obviously the solvent-free product'w'ould be even more so.Surface-activity representing an advanced hydrophile-hydrophobe balancecan also be, determined byjthe use of conventionalme'asiirementsheremarter described. I one outstanding characteristic iproperty'indicating surface-activity in a material is .the ability-toform a permanent foam in dilute aqueous solution, for example, less than0.5%,-

when in the higher oxyalkylated sta ge, and to form an emulsionin thelowerand intermediate sta es"of-oxyalkylation;

Allowance mustbe made for the presence of a; solvent inthe final productin relation to the I hydrophi le-prop' erties of: the final product, The

principle involved in the manufacture of the; herein contemplatedcompounds foruse as-polyhydric reac.tants,- is ibased on the conversionof a hydrophobeiornon-hydrophile compoundormix turegof: compounds intoproducts-which are dis tinctl-y. hydrophile;-at least to the extent-thatthey have emulsifying properties or are self-] emulsifying; that is,-wheni shaken withwater they produce stable or semistable suspensions,

i he. p esence: of a water-insoluble solvent;

such asxylenean emulsion; Indemul'sification, it is sometimes preferableto use a product hav'-" ing. markedly.- enhanced hydrophile propertiesovrrandfabov'e the initial stage ofself-femulsifiability, although wehave found that with prod'-" ucts of the typeus'e'd herein," mostefficaciousre sults are obtained with products which do not havehydrophile properties beyond the stage bf selfdis'persibility;

More highly oxyalkyl'ated resins; give colloidal solutionsor solswhichf'show typical properties "comparable to ordinary surface-activeagent'si Sucheonventional' surface-activity'may be ,measxuredbydetermining thefsurfacejtension and the" interfacialtensi nagainst 'par'afiin on bridle like,

At the miner an lower stages or oxyaikyiauoii,

same manner but mayernploy an emulsiiia cati emulsifying egas; Somesurface -'active emulsi- ,te'st, Emulsionscoine intoexistence' as arule, through the presence of a; surface-active 19' fying agents such asmahogany soap may produce a water-in-oil emulsion or an oil-in-wateremulsion depending upon the ratio of the two phases, degree ofagitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower stage of oxyalkylation, the so-called subsurface-active stage. The surface-active properties are readilydemonstrated by producing a xylenewater emulsion. A suitable procedureis as follows: The oxyalkylated resin is dissolved in an equal weight ofxylene. Such 50-50 solution is then mixed with 1-3 volumes of water andshaken to produce an emulsion. The amount of xylene is invariablysufficient to reduce even a tacky resinous product to a solution whichis readily dispersible. The emulsions so produced are usuallyxylene-in-water emulsions (oil-in-water type) particularly when theamount of distilled water used is at least slightly in excess of thevolume of xylene solution and also if shaken vigorously. At times,particularly in the lowest stage of oxyalkylation, one may obtain awaterin-xylene emulsion (water-in-oil type) which is apt to reverse Onmore vigorous shaking and further dilution with'water.

If in doubt as to thisproperty, comparison with a resin obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1.formaldehyde) using an acid catalyst and then followed by oxyalkylationusing 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.Such resin prior tooxyalkylation has a molecular weight indicating about4 units per resin molecule. Such resin, when diluted with an equalweight of xylene, will serve to illustrate the above emulsificationtest.

In a few instances, the resin may not besufliciently soluble in xylenealone but may require the addition of some ethylene glycol diethyletheras described elsewhere. It is understood that such mixture, or any othersimilar mixture, is

producing a dispersion in water is proof that it is distinctlyhydrophile. In doubtful cases, comparison can be made with thebuty-lphenolformaldehyde resin analog wherein 2 moles of ethylene oxidehave been introduced for each phenolic nucleus.

The presence of xylene or anequivalent waterinsoluble solvent may maskthe point at which a solvent-free product on mere dilution in a testtube exhibits self-emulsification. For this reason, if it is desirableto determine the approximate point where self-emulsification begins,then it is better to eliminate the xylene or equivalent from a smallportion of the reaction mixmaterial to emulsify an insoluble solventsuch as xylene. It is to be emphasized that hydrophile properties hereinreferred to are such as those exhibited by incipient self-emulsificationor the presence of emulsifying properties and go through the range ofhomogeneous dispersibility or admixture with water even in presence ofadded water-insoluble solvent and minor proportions of commonelectrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used todetermine ranges of surface-activity and that such emulsification testsemploy a Xylene solution. Stated another way, it is really immaterialwhether a xylene solution produces a sol or whether it merely producesan emulsion.

In light of what has been said previously in regard to the variation ofrange of hydrophile properties, and also in light of what has been saidas to the variation in the effectiveness of various alkylene oxides, andmost particularly of all ethylene oxide, to introduce hydrophilecharacter, it becomes obvious that there is a wide variation in theamount of alkylene oxide employed, as long as it is at least 2 moles perphenolic nucleus, for producing products useful for the practice of thisinvention. Another variation is the molecular size of the resin chainresulting from reaction between the difunctional phenol and the aldehydesuch as formaldehyde.

It is well known that the size and nature or structure of the resinpolymer obtained varies somewhat with the conditions of reaction theproportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared asherein described, particularly in the absence of a secondary heatingstep, contain 3 to 6 or 7 phenolic nuclei with approximately 4 or 5nuclei as an average. More drastic conditions of resinification yieldresins of greater chain length. Such more intensive resinification is aconventional procedure and may be employed if desired. Molecularweight,'of course; is measured by any suitable procedure, particularlyby cryoscopic methods; but using the same reactants and using moredrastic conditions of resinification one usually finds that highermolecular weights are indicated by higher melting points of the resinsand a tendency to decreased solubility. See what has been said elsewhereherein in regard to a secondary step involving the heating of a resinwith or without the use of vacuum.

We have previously pointed out that either an alkaline or acid catalystis advantageously used in preparing the resin. A combination ofcatalysts is sometimes used in two stages; for instance, an alkalinecatalyst is sometimes employed in a first stage, followed byneutralization and addition of a small amount of acid catalyst in asecond stage. It isgenerally believed that even in the presence of analkaline catalyst, the number of moles of aldehyde, such asformaldehyde, must be greater than the moles ofphenol employed in orderto introduce methylol groups in the intermediate stage. There is noindication that such groups appear in the final resin if prepared by theuse of an acid catalyst. It is possible that such groups may appear inthe finresins prepared by ourselves. Our preferencehowever, is to use anacid catalyized'resin, particularly' employing a for'maldehyde-to-phenol ratio of' 0.95 to 1.20 and, as far as'we havebeenable to determine, such resins are free from methylol groups; As amatter of fact, it is probable that in acid-catalyzed resinifications,the methylol Structure may appear only momentarily at the very beginningof the reaction and-in all probability" is converted at once into amore" complex structure during the intermediate stage.

One procedure which can 'be employed in the use'of a new resin toprepare polyhydric reactants for use in the preparation of'compoundsemployed in the present invention, is to deter mine the hydroxyl valueby the Verley-Bdlsing method or its equivalent. The resin as such, or inthe form of a solution as described, i then treated with ethylene oxidein presence of 0.5 to 3% of sojdium'methyla'te as a' catalyst instepitiselfashiom The conditions of reaction, as far as time or per centare concerned, are within Ithe'range previously indicated. With suitableagitationthe ethylene oxide, if added'in'molecular' proportion,combineswithin a comparatively short time, for instance a'few minutes to2 to 6 hours, but insome instances requires as much fafsB to 24 hours."A useful temperature range is from 125to 225 C; The completion of'thereactionof each addition of ethylene oxide in step wise fashionis'usually indicated by the reduction or' elimination of pressure. ""Anamount conveniently used for eac "addition is generally equivalent to amole or'two moles of ethylene oxide :per' hydroxyl radical. When the"amount of ethyle ne"ox'ide added" is equivalent map;

proximately.5b% byweight of theioriginal res sampieis'teistedifo'r[incipient'hydrophilep' a t y mf l hak ng 1 at as s or a ter he m aon f h pivf .tfl e eem amen Th were? 9 r se X Qe-H to obtain us u 1mu1si 1n e t see-gr m varies from 70% by weight of the original resin toas much as five or six times the weightsof the original resin. In thecase of: aresin'derived from para-tertiary .butylphenol, as1ittle=asg50% by Weightof ethylene:- oxidei'may .give suitablesolubility. With propylene oxide; :even a greater molecular proportionis required: and sometimes a resultant of only limited hydrophileproperties i's'obtainable'. The same-is true to even" a greater extentwith butyIene' oXide. 'The hydroxylated alkylene oxides aremoreeffective' in solubilizing properties than the comparablecompoundsin which no h-ydroxyl "is-present.-

Atte'fitio n' i's' directed'to' the 'fact' that in the subsequentexamples reference is made to the stepwise "addition of the' alkyleneoxidef'such as ethylene oxide. It is understood, of course', 'there is"no 'objeetion'to thecontinuous 1 addition of al; kyleneoxideuntil'the'ldesired stageofreaction is're ached. In fact, theremaybe lessof a -hazard involve'df'and itis often adyantageeusfto add thelk 'r ox -Q sl w 'inaeqnt u s f e mfa d misuc mq nrasi s jfx mgi eh piessuresnttedfin theivario "xamples or he -I3 f 1 j .f. I It may be "wellto. emphasizethe fact that, when r fil s "ii li d I O Y ififi fi mm h lbE and some of the higher aliphatic 1 aldehydes, such a e d h damhe r ua t i a'cbmba eti v si 0. ile kerssi at q d r ar mp ratiires; uch r'blqeme comp ti -fl id at 0? s. hi5? Mela as thi s'qan be readilykylated, preferably w'r a 'i e i ei t vs 1 in a r. fo

instanee the depth of atesttube,

yields 'a product which: will give,

' by-weight, and a third example using about 500% 22 oxyethylated,without the use ofa solvent;

What has been said previously is not intended to suggest that anyexperimentation is necessary to determine the degree of oxyalkylation,and particularly oxyethylation. What has been said previously is'submitted primarily to emphasize the fact that these remarkableoxyalkylated resins'having surface activity show unusual propertiesas'the hydrophile character varies from a' minimum to an ultimatemaximum. One should not underestimate the utility of any of theespolyhydric alcohols in a surface-active or sub-surface -active rangewithout examining them 'by" reaction with a'number of the typical acidsherein described and subsequently examin ing the resultant for utility,either in demulsificationor in some other art or industry as referredto" elsewhere, or as a reactant for the manufacture of more complicatedderivatives. A few simplelaboratory tests which can, be conducted inaroutine manner will usually give all the in fpr'mationthat is required.

For instance, a simple rule to follow is to prepare "a resin having atleast three phenolic nuclei and being organic solvent-soluble.Oxyethylate such resin, using the following four ratios of moles ofethylene oxide per phenolic unit equivalent: 2 to 1;'6 to 1; 10'to I;and15 to 1. From a sample of each product remove any solvent that may bepresent, s'uch as xylene. Prepare 0.5% and 5.0% solutions in distilledwater, as previously indicated. A mere examination of such series willgenerally reveal an approximate range of minimum hydrophile character,moderate hydrophile character, and maximum hydrophile character. If the2 tol ratio does not show minimum hydrophile character by test of thesolvent-free product, then one should test its capacity to form anemulsion when admixed, with xylene another insolublesolvent; If neither.test shows. therequ ired minimum hydrophilef p op erty,repetitionusi'ngi 2 /2 to. 4 moles per: phenolic nucleus 'willfjserveh'Moderate hydrophile. chair.- acter shouldbe shown byeither the.6'to,l or10 ix) 1 ratioQ Such moderate. hydrophile character is i ndic ated bythe .factfthat. the sol distilled water \within, the' previouslymentioned conce n tratio orange H is a [permanent translucent. sol

I I e Ultimate dropl ilecharacter. is usually shown: at the l 5 to l.ratio test in,that adding a small amount of aninsoluble solventpiorinstance 5% of xylene,

r at least temporarily, a transparent or translucent sol oi the kind f,i 1 st described. aThe formation of a per: manent,foam,-when a 0.5%to:5.0%v aqueous solution isQshaken, is -anr excellent test. for surfaceactivity. Previous reference," has been made ,to

the tact thatgother ,oxyalkylating agent may. requirethe use of;increased amounts ofalkylene oxide. -.-However,.if one, does not eyencare togo to the trouble of. calculating molecular weights,

one-can simply-arbitrarily prepare compounds containing ethylene oxideequivalent to about 50% -to-;'75% by weight, for example %:by weight, ofthe resin to be oxyethylatedyaxsecand example "using approximately 200%''1 30'?'300 to; 750%:by-weight, to explore. the range. of'hydrophile+hydrophobe balance. r

A rac cai exam ati n; of: t e fa t 56: exit-1 allsrlatian l ysl mad :bya ray s mpletest using a pilotplanti autoclave; having ascapacity ofabout to gallons as hereinafter described. Such, laboratory preparedroutine compounds can then betested for solubility and, generallyspeaking, this isgall that is required to give asuitable;varietygcovering the hydrophilehydrophobe range. All-thesetests, as stated, are intended to be routine ;,tests and ,nothingqmore,They are intended to teacha person,,even ;though unskilled inoxyethylation or oxyallwlation, how to prepare in-a perfectly arbitrarymanner, a series of compounds illustrating the hydrophilehydrophoberange. v 1

If one purchases a thermoplastic or--fusible resin on the open marketselected from a suitable number which are available, one might have tomake certain determinations in order to make the quickest approach tothe appropriate oxyalkylation range. For instance,.one should know (a)the molecular size, indicating the number of phenolic units; (2))thenature of the aldehydic resa idue,.which is usually. CH2; and (c) thenature of the substituent, which is. usual1y butyl. amyl, or phenyl.With such information one isin substantially the same position as ifone'had personally madethe resin prior to oxyethylation.

For instance, the molecular weight of the internal structural units ofthe resin of the following over-simplified formula I OH OH IOH h H r. H

(nzl to 13. or even more) 1 is given approximately by the formula: (Mol.wt. of phenol 2) plus mol. wt. of methylene or substituted methyleneradical. The molecular weight of the resin would be n times. the valuefor the internal limit plus the values for the terminal units. Theleft-hand terminal unit of the above structural formula, it will beseen, is identical with the recurring internal unit except that it hasone extra hydrogen. The right-hand terminal unit lacks the methylenebridge element. Using one internal unit of a resin a the basic element,a resins molecular weight is given approximately by taking (it plus 2)times the weight of the internal element. Where the resin molecule hasonly 3 phenolic nuclei as in the structure shown, this calculation willbe in error by several per cent; but as it grows larger, to contain 6,9, or 12 phenolic nuclei, the formula. comes to be more thansatisfactory. Using such an approximate weight, one need only introduce,for example, two molal weights of ethylene oxide or slightly more, perphenolic nucleus, to produce a product of minimal hydrophile character.Further oxyalkylation gives enhanced hydrophile character. Although wehave prepared and tested a large number of oxyethylated products of thetype described herein, we have found no instance where the use of lessthan 2 moles of ethylene oxide per phenolic nucleus gave desirableproducts.

Examples lb through 18b, and the tables which appear in columns 51through 56 of our said Patent 2,499,370 illustrate oxyalkylationproducts from resins which are useful as intermediates for producing theesterified products used in accordance with the present application,

24 such examples giving exact and complete details for carrying out theoxyalkylation procedure.

.Theresins, prior ,to oxyalkylation, vary from tacky, viscous liquids tohard, high-melting solids. Their color varies from a, light yellowthrough amber,'to a; deep red or even almost black. In

.the manufacture of resins, particularly hard resins asthe reactionprogresses the reaction mass frequently goes through a liquid state to asub-resinous or semi-resinous state, ofter characterizedby being tackyor sticky, to a final complete resin. As the resin issubjected tooxyalkylation these same physical changes tend to take place in reverse.If one starts with a solid resin, oxyalkylation tends to make it tackyor semi resinous and further oxyalkylation makes the tackiness disappearand changes the product to a liquid. Tl iu's, asthelresin isoxyalkylated it decreases-inviscosity, that is, becomes more liti-vuidor changes fromla solid to a liquid, particularlywhen it isconvertedto the water-dispersible'or'wat'er solublestage. The coloroftheoxyalkylated derivative isusually considerably lighter thanthe originalproduct from which. it is made, varying from a, pale .straw color to anamber .or reddish amber. The, viscosity usually varies from" that of anoil, like 'castor oil, to that of a thick viscous sirup. Some productsare waxy. The presence of a solvent, such as 15% xylene or thelike,.thins the viscosity considerably and also reduces the color indilution. No undue significance need be attached to the color for thereason that if the same compound is prepared in glass and in iron,thelatter'usually has somewhat darkercolor. If the resins are preparedas customarily employed in varnish resin manufacture, i. e.,,a procedurethat excludes the presence of oxygen during the resinification andsubsequent cooling of the resin, then of course the initial resin ismuch lighter in color. We have employed some resins which initially arealmost water-white and also yield a lighter colored final product.

Actually, in considering the ratio of alkylene oxide to add, and we havepreviously pointed out that this can be predetermined using laboratorytests, it is our actual preference from a practical standpoint to maketests on a small pilot plant scale. Our reason for so doing is that wemake one run, and only one, and that we have a complete series whichshows the progressive effect of introducing the oxyalkylating agent, forinstance, the ethyleneoxy radicals. Our preferred procedure is asfollows: We prepare a suitable resin,

or for that matter, purchase it in the open mar-- ket. We employ 8pounds of resin and 4 pounds of xylene and place the resin and xylene ina suitable autoclave with an open reflux condenser. We prefer to heatand stir until the solution is complete. We have pointed out that softresins which are fluid or semi-fluid can be readily prepared in variousways, such as the use of ortho tertiary amylphenol, orthohydroxydiphenyl, ortho-decylphenol, or by the use of higher molecularweight aldehydes than formaldehyde. If such resins are used, a solventneed not be added but may be added as a matter of convenience or forcomparison, if desired. We then add a catalyst, for instance, 2% ofcaustic soda, in the form of a 20% to 30% solution, and remove the waterof solution or formation. We then shut off the reflux condenser and usethe equipment as an autoclave only, and oxyethylate until a total ofpounds of ethylene oxide have been added, equivalent to 750% of theoriginal resin,-

25 We preferv a temperature of about 150 C. to 175 C. We also takesamples at intermediate points as indicated in the following table:

Oxyethlation to 750% can usually be completed within 30 hours andfrequently more quickly;

The samples taken are rather small, for instance, 2 to 4 ounces, so thatno correction need be made in regard to the residual reaction mass. Eachsample is divided in two. One-half the sample is placed in anevaporating dish on. the steam bath overnight so as to eliminate thexylene. Then 1.5% solutions are prepared from both series of samples, i.e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be siifiicient toindicate hydrophile character or surface activity, i. e., the product issoluble, forming a colloidal sol, or the aqueous solution foams or showsemulsifying property. All these properties are related throughadsorptionat the interface, for example, a gas-liquid interfaceor aliquid-liquid interface. If desired,

surface activity can be measured in any one of the usual ways using a DuNouy tensiometer or d in p e. or a y, bth P dure t r measuringinterfaoial tension. Such tests are conventional and require no furtherdescription. Any compound having fsub-surface-activity, and all derivedfrom the same resin and oxyalkylated to a greater extentri; e., thosehaving a greater proportion of alkylene oxide; are useful, as polyhydricreactants for the practice of this invention.

Another reason why we prefer to use a plant test of the kind abovedescribed is thatwe can use the same procedure to evaluate tolerancetowards a trifunctienalphenolsuch as hydroxy: be z n o i ies ssol a iiac r v. r i s reference has beenmade to thefact that one can conduct alaboratory scale test which will indicate whether or not a resin,althoughsoluble in solvent, will yield an insoluble rubbery product, i.e., a product which is neither hydrophile nor surface-active, uponoxyethylation, particularly extensive oxyethylation.. It is also obviousthat. one may have a solvent-soluble resin derived from a mixture ofphenols having present 1% or 2% of a trifunctionalphenol whichuw illresult in an insoluble rubber at the ultimate stages of oxyethylat ionbut not in the earlier stages. In other ,words, with resins from some suh p e s a di io 1.2. m le o t eoryalkylating agent per phenolicnucleus,particular y. e hylene. oxide i s a surface-activ r actantwhichisperfectlysatisfactory; while more extensive oxyethylationyieldsaninsoluble rubber, th'atis, an unsuitable reactant. ,Itisobface-active.

26 vious that this present procedure of evaluating trifunctional phenoltolerance is more suitable than the previous procedure.

It may be well to call attention to one result which may be noted in along drawn-out oxyalkylation, particularly oxyethylation, which wouldnot appear in a normally conducted reaction. Reference has been made tocross-linking and its eifect on solubility and also the fact that, ifcarried far enough, it causesincipient stringiness, then pronouncedstringiness, usually followed by a semi-rubbery or rubbery stage.Incipient stringiness, or eve pronounced stringiness, or even thetendency toward a rubbery stage; is not objectionable so long as thefinal product is still hydrophile and at least sub-sun- Such materialfrequently is best mixed with a polar solvent, such as alcohol or thelike, and preferably an alcoholic solution is used. The point which wewant to make here, however, is this: Stringiness or rubberization atthis stage may possibly be the result of etherification. Obviously if adifunctional phenol and an aldehyde produce a non-crosslinked resinmolecule and if such molecule is oxyalkylated so as to introduce aplurality of hydroxyl groups in each molecule, then and in that event ifsubsequent etherification takes place, one is going to obtaincross-linking in the same general way that one would obtaincross-linking in other resinification reactions. Ordinarily there islittle or no tendency toward etherific'ation during the oxyalkylationstep. If it does take place at all, it is only to an insi griificant andundetectable degree. However, suppose that a certain Weight of resin istreated withan equal weight of, or twice its weight of; ethylene oxide.This may be done in a comparatively short time; for instance, at 15 0 or175 C. in 4 to 8 hours or even less. On the other hand, if in anexploratory reaction, such as thekind previously deseribed, the ethyleneoxide were added extremely slowly in order to take stepwise samples,sothat the reaction required 4 or 5 times as long to introducean equalamount of ethylene oxide. employing the same temperature, thenetherification might cause stringiness or a suggestion of rubberiness.For thisreason if in an exploratory experiment of the kind previouslydescribed there appears to be any stringiness or rubberiness, it may beWell to repeat the experiment and reach the intermediate stage ofoxyalkylation as rapidly as possible and then proceed slowly beyond thisintermediate stage. Theentire purpose of this modified procedure is tocut down the time of reaction so as to avoid etherification if it becaused by the extended time period. I I

It may be well. to note one peculiar reaction sometimes noted in thecourse of oxyalkylation, particularly oxyethylation, of thethermoplastic resins herein described. This effect is noted in 7 v acase where a thermoplastic resin has been oxyalkylated, forinstanceoxyethylated, until it gives a perfectly clear solution, e venin the presence of some accompanying water insoluble solvent such as 10%to 15% of xylene. Further oxyalkylation, particularly oxyethylation, may

then yield a product which, instead of giving a clear solution aspreviously, gives a very milky solution suggesting that some markedchange has taken place. One explanation of the above change is that thestructural unit indicated in the following way where 8n is a fairlylarge numher, for instance, 10 to 20, decomposes and an HC JH HCH Thisfact, of course, presents no difficulty for the reason thatoxyalkylation can be conducted in each instance stepwise, or at agradual rate, and samples taken at short intervals so as to arrive at apoint where optimum surface activity or hydrophile character is obtainedif desired; for products for use as 'polyhydric reactants in thepractice of this invention, this is not necessary and, in fact, may beundesirable, i. e., reduce the efficiency of the product.

We do not know'to what extent oxyalkylation produces uniformdistribution in regard to phenolic hydroxyls present in the resinmolecule. In some instances, of course, such distributio can not beuniform for the reason that we have not specified that the molecules ofethylene oxide, for example, be added in multiples of the units presentin the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum oftwo moles of ethylene oxide per phenolic nucleus are added, this wouldmean an addition of moles of ethylene oxide, but suppose that one added11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, evenassuming the most uniform distribution possible, some of thepolyethyleneoxy radicals would contain 3 ethyleneoxy units and somewould contain 2. Therefore, it is impossible to specify uniformdistribution in regard to the entrance of the ethylene oxide or otheroxyalkylating agent. For that matter, if one were to introduce 25 molesof ethylene oxide there is no way to be certain that all chains ofethyleneoxy units would have 5 units; there might be some having, forexample, 4 and 6 units, or for V that matter 3 or '7 units. Nor is thereany basis for assuming that the number of molecules of the oxyalkylatingagent added to each of the molecules of the resin is the same, ordifferent. Thus, where formulae are given to illustrate or depict theoxyalkylated products, distributions of radicals indicated are to bestatistically taken. We have, however, included specific directions andspecifications in regard to the total amount of ethylene oxide, or totalamount of any other oxyalkylating agent, to add.

In regard to solubility of the resins and the oxyalkylated compounds,and for that matter derivatives of the latter, the following should benoted. In oxyalkylation, any solvent employed should be non-reactive tothe alkylene oxide employed. This limitation does not apply to solventsused in cryoscopic determinations for obvious reasons. Attention isdirected to the fact that various organic solvents ay be employed toverify that the're'sin is organic solvent-soluble. Suchsolubility testmerely characterizes the resin. The particular solvent used' in "suchtest may not be suitablefor a molecular weight determination and,likewise, the -solven't used in 28 determining molecular weight may notbe suitable as a solvent during oxyalkylation. For solution of theoxyalkylated compounds, or their derivatives a great variety of solventsmay be employed, such as alcohols, ether alcohols, cresols, phenols,ketones, esters, etc., alone or with the addition of water. Some ofthese are mentioned hereafter. We prefer the use of benzene ordiphenylamine as a solvent in making cryoscopic measurements. The mostsatisfactory resins are thosewhich are soluble in xylene or the like,rather than those which are soluble only in some. other solventcontaining elements other thancarbon and hydrogen, for instance, oxygenor chlorine. Such solvents are usually polar, semi-polar, or slightlypolar in nature compared with xylene, cymene, etc.

- Reference to cryoscopic measurement is concerned'with the use ofbenzene or other suitable compound as a solvent. Such method will showthat conventional resins obtained, for example, from para-tertiaryamylphenol and formaldehyde in presence of an acid catalyst, will have amolecular weight indicating 3, 4, 5 or somewhat greater number ofstructural units per molecule. Ifmore drastic conditions ofresinification are employed or if such low-stage resin is subjected to avacuum distillation treatment as previously described, one obtainsaresin of a distinctly higher molecular weight. Any molecular weightdetermination used, whether cryoscopic measurement or otherwise, otherthan the conventional cryoscopic one employing benzene, should bechecked. so as to insure that it gives consistent values on suchconventional resins as a control. Frequently all that is necessary tomake an approximationv of the, molecular weight range is to make acomparison .with the dimer obtained by chemical combination of two molesof the same phenol and one mole of the same aldehyde under conditions toinsure dimerization. As to the preparation of such dimers fromsubstituted phenols, see Carswell, Phenoplasts, page 31. The increasedviscosity, resinous character, and decreased solubility, etc., of thehigher polymers in-comparisonwith-the dimer, frequently are all that-isrequired to establish that the resin contains 3 or more structural unitsper molecule.

Ordinarily, the oxyalkylation is carried out in autoclaves provided withagitators or stirring devices. We have found that the speed of theagitation markedly influences the reaction time. In some cases, thechange from slow speed agitation, for example, in a laboratory autoclaveagitation with a stirrer operating at a speed of 60 to'2 0() R'. P. M.,tohigh speed agitation, with "thestirrer'operating at 250 to 350 R. P.M., reducesthe time required for oxyalkylation by about One half' totwo-thirds. Frequently xylene soluble products which give insolubleproducts by' proc'edui e's' employing comparatively slo'w speed'agitatiom give suitable hydrophile products when produced by similarprocedure butwith highspeedagitation -as a result;- we believe,'- of the'i'duction in the time required opportunity for .curing or etherization;Even if the formation of an insoluble product is not involved, it isfrequently advantageous to speed up the reaction; thereby: reducingproduction time; by increasing agitating speed. In large scaleoperations, we have demonstrated that coo nomical manufacturing res ltsfrom continuous oxyalkylation, that is,' an operation in which thealkylene oxide is continuously fed to the reaction vessel, with highspeed agitation; i; e., an agi tator operating at 250 to 350 R. P. M.Continuous oxyalkylation, other conditions being the same, is more rapid.than batch oxyalkylation, but the latter is ordinarily more convenientfor laboratory operation; i I

Previous reference has been made to the fact that in preparing esters orcompounds of the kind herein described, particularly adapted fordemulsification of water-in-oil emulsions, and for that matter for otherpurposes, one should make a complete exploration of the wide variationin hydrophobe-hydrophile balance as, previously referred to. It has beenstated, furthermore, that this hydrophobe-hydrophile balance of theoxyalkylated resins is imparted, as far as the range of variation goes,to agreater dr lesser extent to the herein described derivatives. Thismeans that one employing the present invention should take the choice ofthe most suitable derivative selected from a numberorrepresenta; tivecompounds, thus, not only should a variety of resins be preparedexhibiting a variety of oxyalkylations; particularly oxyethylations, butalso a variety of derivatives. This can be done conveniently in light ofwhat has been said previously. From a practical standpoint, using pilotplant equipment, for instance, an autoclave h aving a capacity ofapproximately three to five gallons. We have made a singlerunby appropriate selections in which the molal ratio of resin equivalent toethylene oxideis one toone, 1 to 5, 1 to 10, 1 to 1-5, and 1 to 20.Furthermor'e, in making these particular runs wehaveused continuousaddition of ethylene oxide. In the con tinuous addition of ethyleneoxide we have employed either a cylinder of ethylene oxide without addednitrogen, provided that the pressure of the ethylene oxide wassufiiciently great to pass into the autoclave, or else we have used anarrangement which, in essence, was the equivalent of an ethylene oxidecylinder with a means for injecting nitrogen so as to force out the 7Bulletin No. 2087 issued in194'7, with specific" ethylene oxide in themanner of 'an ordinary Seltzer bottle, cbmbined with the means foreither weighing the cylinder or measuring the ethylene oxide usedvolumetrically. Such procedure and arrangement for injecting liquids is,oilcourise, conventional. The following data sheets exemplify suchoperations, i. e., the combinationpf both continuous agitation andtaking sampleis so 'as to give five difierentvariants in oxyethylation.In adding ethylene oxide continuously, there; is one precaution whichmust be taken at all times. The addition of ethylene oxide must stopmmediately if there is any indication that reaction is stopped or,obvious'ly, ifre'actien is started at the' beginning of the reactionperiod; since the addition of ethylene oxide is invariably an exothermicreaction, whether or not reaction has taken place can be judged in theusual manner by observing (a) 1, temperature rise cir drop, if any,

(1)) amount of cooling water orother meansre: quired to dissipate heatof reaction; thus, if there is a temperature drop without'the use ofcooling water or equivalent, or if there is no rise in temperaturewithout, using cooling water control, careful investigationshould bemade.

In the tables immediately following, we are showing the maximumtemperature which is iisually the eperating temperature. In other words,by experience we have, found that if the initial reactants are raised tothe indicated temperature and then if ethylene oxide is added slowly,this temperature is maintained by cooling water until thefoxyethylati'on is complete. We have also indicated the maximumpressurethat we obtained or the pressure range. Likewise, we haveiiidicated the time required to inject the ethylene oxide as well as abrief note as to the solubility of the product at the end of theoxy-.ethylation period. As one period ends it'will be noted we haveremovedpart of the oxyethylated mass to give us derivatives, as thereindescribed; the rest has been subjected to further treatment. All this isapparent by examining the columns headed fitarting mixj .Mix atend ofreaction? Mix which is removed for sample, and Mix which remains as nextstarter.

The resins employed are prepared in the man ner described in Examples 1athrough 103a of our said Patent 2,499,370, except that instead of beingprepared on a laboratory scale they were prepared in 10to.15-gallonelectro-vapor heated synthetic resin pilotplant reactors, asmanufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, andcompletely described in their reference to, SpecificatienNo.11153965.

For convenience, the following tables give the numbers of the examplesofour .said Patent 2,499,370 in which the preparation of identical resins'pn'laboratoryscaie are described. It is understood that in thefollowing examples, the change is one with respect to the size of theoperation, 7 r

The solvent used in each instance was xylene. This solvent isparticularly satisfactory fer the reason that it can be removed readilyby distillation or vacuum distillation. In these con tinuous experimentsthe speed of the stirrer in the autoclave was 250 R. P. M. i i i Inexamining the subselquent tables it will be noted that if acomparatively small sample is 7 taken at each stage, for instance, toone gallon, one can proceed through theentire molal stage of 1 to l, tol to 20, without remaking at any intermediate stage. This is illustratedby Example l04b. In other examples we found it desirable to take alarger sample,, for instance, a 3- gallon sample; at an intermediatestage- As a result it was necessary in such instances tosta'rt with anew resin sample in ordertoprepare suificient oxyethylated derivativesillustrating the latter stages. Under such circumstances, of course,'theearlier stages which had been previouslyprepared were by-passed orignored, This is illustrated in theta'bles" Where, obviously, it

shows that the starting mix was not removed from a previous sample. I

ens-41,995 f v g 31 r 32 Phenol for resin: Para-tertiary amylphenolAldehyde for resin: Formaldehyde Date, June 22, 1948 [Resin made inpilot plant size batch, approximately 25 pounds, corresponding to 3a ofPatent 2,499,370 but this batch designated 104a,]

. Mix Which is Mix Which Re- Starting Mix Mlx at End of Removed formains as Next Reaction Sample Starter Max Max 7 Pressure, TemperafiSolubility lbs sq in ture gbis. abs. Lbs Ifibs. Lbs abs. Lbs gbis. 115.Lbs

o eso eso eso esvent in Eto vent in Etc vent in Eto vent in 1 FirstStage Resin to EtO Molal Ratio 1'. 14 15.75 0 14.25 15.75 4.0 3.35 3.651.0 10.9 12.1 3.0 80 150 $4 I Ex. N0.104b

Second Stage Resin to EtO. Molal Ratio 1: 10. 9 12.1 3.0 10. 9 12.1 15.25 3. 77 4. 17 5.31 7.13 7.93 9. 94 158 P ST Ex. No.105b. I

Third Stage Resin to 15120.- I Molal Ratio 1:10. 7 13 7.93 9. 94 7.13 7.93 19. 69 3.29 3.68 9.04 '3. 84 4.25 10. 65 60 173 FS Ex. No. 106b-Fourth Stage Resin to EtO. Molal Ratio 1:15. 3 84 4.25 10.65 3.84 4.2516.15 2. 04 2.21 8.55 1.80 2.04 7.60 220 160 RS Ex.N0.107b

Fifth Stage Resin to EtO Molal Ratio 1:20- 1 2. 04 7. 60 1.80 2.04 10.2QS' Ex. N0.108b

1=Insoluble. ST Slight tendency toward becoming soluble. FS Fairlysoluble. RS Readily soluble. QS Quite soluble.

Phenol for resin: N onylphenol Aldehyde for resin: Formaldehyde Date,June 18, 1948 [Resin made in pilot plant size batch, approxunately 25pounds, corresponding to 70a of Patent 2,499,370 but this batchdesignated 10971.]

. Mix Which is Mix Which Re- Starting Mix figg figg' of Removed formains as Next 4 Sample Starter Max. Max. Time I Pressure, TempgrahmSolubility LbIS. Ifibs. Lbs i b s. I bs. Lbs lbls. ns. Lbs ge s. Ifibs.Lbs 50-, es- 0- es- 0- es- 0- esvent in MO vent in Eto vent in Eto ventin Eto First Stage Resin to Et0 Molal Ratio 111-- 15 0 15.0 0 15.0 15.03 5.0 5.0 1.0 10.0 10.0 2.0 50 150 1% ST Ex. No. 109b.

Second Stage Resin to EtO. Molal Ratio 1:5" 10 10 2.0 10 10 9.4 2.72 2.72 2.56 7. 27 7. 27 6.86 100 147 2 D'I Ex. N0. 11%..

Third Stage Resin to EtO Molal Ratio 1' 7. 27 7 27 6. 86 7. 27 7. 2713.7 4.16 4. 16 7. 68 3.15 3.15 5.95 125 1% S Ex. No. 111b.

Fourth Stage Resin to EtO. Molal Ratio 1: 3 15 3. 15 5.95 3.15 3. 15 8.95 1. 05 1.05 2. 95 2.10 2. 10 6.00 220 174 2% S Rx. No. 112b FifthStage Resin to EtO Molal Ratio 2.10 2.10 6.00 2.10 2.10 8.00 220 183 3%;VS Ex. No. 113b S =So1uble. ST= Slight tendency toward solubility.DT=Definite tendency toward solubility. VS=Very soluble.

Phenalfar mm Parakoetylphenbl.

Date, June 23, 24, 1948 Aldehyde for main: Formaldehyde [Resin mades in.pilotplanhsiz'e batcmapproximately- 25 pofinds -eonespondingjw 8a oiPatent.2,499;370-but thisbatchdesignated 1'14a.]

l Mix Which isi MIX Which.Re- Starting Mix gig ggg v Removed m1 mains'asNxf Sample- Starter v Max. Max. Time v Pressur e,- ;-Temp erahrs.Solubility Tszbls". I 'bs; l lsubls. gas. Lbs ge s. tbs 'lbls. 1. W

es 0-- es 1- o- 0-- es-- vent in vent:v in Event: in Eta Went in Eta 1First Stage Resin to EtOL V a t MolaLRatio 1412 15.8 1.0 14.2 115.8- *i3.25 i 3.1 354 i 0.75 11.1% 3.12.4 E v21R 50': 150' 1%: NS Ex. No.1141).. Y

Second Stage Resin to EtOl.-. f 1. Molali Ratio 1111' 12.4 2.5 11.1 12.4512.5? 7.0 .71825 7.882 4.1: Z 4358; 4.6215 1001 17]: M SS Ex. NO. 115b.Q

Third Stage I Resin to Et0.. Molal Ratio 61-64 7. 36 z 0 6.621.7.36.151! 120i 190 136- S Ex. No. 116b g Fourth Stage Resin to moi. kMolal: Ratio 1?:15. 40 4.9 0. 4.4. 4.9 .14.8: r 4110; 160.. 3'2 VS Ex.No. 1171;"--- g 5 Fifth Stage Resin to EtOL"- F v Molal: Ratio L220. 4114. 58 j 4. 62 4. 1 4.58 1R 260 r 172 9!; VS Ex. No. 118b 1 g S= Soluble.NS =Not soluble. SS=Samvawhzemsoluble. .VS=Verysulubl.-

Phemlifawaresin: -iMe'nthy tp hen-01' Date, July 8-13, 1948 [Resinmadeimpilotplant sizebafchi approximately'fi-tpaunds; currasponding iuammnfatent'2;490,370 1mt:this batch-designatedlwml Aldehyde fvriresimFormaldehyde 1 a Mix Whlchi's' Mik WhichRe- Starting Mix 2 g lt 5 2.R'emovdion mains'asN'ext Sample: Starter Max. Max. Time Pressu e,Tempsra- Solubility Lbs. Lbs; Lbs. l mus. Lbs; Sol- Res- Egg- Soli Sjol-:R se s01 vent in vent;v inv vent in First Stage v Resin to EtO 1 I I:MdlaliRaLiul': 13:65 16.85 (I 13.65 216.355 350' 2 9.55. 1.14.51 2.1 34:1 2' 4:9? 0.9: 160 1% NS Ex. N0. 11%... f

Second Stage Resin to EtOL--- I Mblal-Ratid 1 15.. 10" 12 0' 10 12-D175? 4.523 5.42; 4.811% 5.4813 6.53.? 5:911 140. 160 1%: S EX. No.l20b..-.

Third Stage Resin to EtO'L". Molal Ratio I:10 5348 6. 58 .i 5. 94 5.485.58 .1035 $4 3 Ex. No. 1210"..- 7

Fourth Stage Resin to EtOL.-. MolahRatiohlS. 4&1 4.9 i 019 4.1-. 5 4.95:r1313 1 180 171 1542 VS Ex. N0. 1221).--

Fifth Stage Resin to EtO' Molal Ratio 1:20. 43210 3.72 0.68 3.10v 3.121343 320 l VS Ex. No. 123i).-."

S=Soluble. VS=Very soluble.

NS =Not soluble.

Phenol for resin: Para-secondat'y butylphenol Aldehyde for 'esin:Formaldehyde Date, July 14-15, 1948 [Resin made in pilot plant sizebatch, approximately 25 pounds, corresponding to 2a of Patent 2,499,370but this batch designated 12411.]

Mix Which is Mix Which Re- Starting Mix figg ggg of Removed for mains asNext Sample Starter Max M Time Pressu e. Temp era- Solubility Lbs. Lbs.Lbs. Lbs. Lhs. Lbs. Lbs. Lbs. Sol- Res- Egg- Sol- Res- 3 83 Sol- Resg fiSol- Res- Egg vent in vent in vent in vent in First Stage Resin to EtOMolal Ratio 111-- 14 15.55 0 14.45 15.55 4.25 5.97 6.38 1.75 8.48 9.172.50 150 54: NS Ex. N0. 1240 Second Stage Resin to EtO Molal Ratio 1:5..848 9.17 2.50 8.48 9.17 16.0 5.83 6.32 11.05 2.65 2.85 4.95 95 188 34 SSEx.No.125b

Third Stage Resin to EtO. Molal Ratio 1:10. 4.82 5.18 0 4.82 5.18 14.25400 183 $5 8 Ex.No.126b

Fourth Stage Resin to EtO Molal Ratio 1:15 3.85 4.15 O 3.85 4.15 17.0120 180 VS Ex. No. 1270 Fifth Stage Resin t0 EtO Mole! Ratio 1:20 2.652.85 4.95 2.65 2.85 15.45 170 1z VS Ex.No.128b

S=Soluble. NS =Not soluble. SS=Somewhat soluble. VS==Very soluble.

Phenol for resin: M enthyl Aldehyde for resin: Propionald'ehyde Date,August 12-13, 1948 [Resin made on pilot plant size batch, approximately25 pounds, corresponding to 81a of Patent 2,499,370 but this batchdesignated 1295.]

- Mix Which is Mix Which Re- Starting Mix gg figg of Removed [or mainsas Next Sample Starter Ma x. Max. Time Pressnye, Temp erahrs Solubilitylbls. g. Lbs 1 .5 3. abs. Lbs lhls. Ifibs. Lbs 1 5 s. I bs. Lbs

oes- 0- es- 0- es- 0- esvent in Eto vent in Eto vent in Eto vent in EtoFirst Stage Resin to EtO Molal Ratio 1:1-- 12.8 17.2 12.8 17.2 2.75 4.255.7 0.95 8.55 11.50 1.80 110 150 Not soluble. Ex. No. 1295 Second StageResin to Et0 Molal Ratio 1:5 85511.50 1.80 8.55 11.50 9.3 4.78 6.42 5.23.77 5.08 4.10 170 $6 Somewhat Ex. N 0. b uble.

Third Stage Resin to EtO Molal Ratio 1:10- 3 77 5.08 4.10 3.77 5.08 13.1100 182 M Soluble. Ex. No. 131!) Fourth Stage Resin to EtO- Molal Ratio1:15- 5.2 7.0 5.2 7.0 17.0 3.10 4.17 10.13 2.10 2.83 6.87 200 182 y.Verysoluble. EX. N 0. 1320----" Fifth Stage Resin to EtO Molal Ratio1:20. 2.10 2.83 6.87 2.10 2.83 9.12 90 $6 Verysoluble. Ex. N o.1335---.--

v 2,541.;995 v U 37 38 Phenol for resi'nf Para-tertiary ainylpheitolAldehyde forre'sin: Furfural Date, August 27-31, 1948 [Resin made onpilot plant size batch, approximately pounds, corresponding to 42a ofPatent 2,499,370 butthis batch designated as 134m] Mix Which is MixWhich Re- Starting Mix at End of Removed for mains as Next 1 ReactionSample Starter Max Max b Time,

Pressu -e, Tempsra- 111$ Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.Lbs.

Sol- Res- Sol- Res- Sol- Res- Sol- Resvent in vent in vent in vent inFirst Stage Resin to EtO V V Molal Ratio 1:1 11.2 18.0 11.2 18.0 3.52.75 4.4 0. 85- 8.45- 13.6 2. 65' 120 135 36 Not soluble. Ex. No. 134!)v b Second .Stage Resin to EtO. v v Molal Ratio 1:5- 8. 13.6 2.65 8.45136 12.65 5.03 8.12 '7. 3.42 6.48 5.10 Y 110v 150 $4 somewhat Ex. N o.135!) soluble.

Third Stage Resin to EtO V Molal Ratio 1:10 4 5 8.0 4. 5 8.0 14. 5 2.454. 35 7. 99- 2. 05 3. 65 6. 180 163 $2 Soluble.- Ex. N0. 136!) FourthStage Resin to EtO V Molal Ratio 1:15-. 3. 42 5. 48 5.10 3.42 5.48 15.10180 7 188 $6 Very solubIe. Ex. No. 137!) Fifth Stage Resin to EtO VMolai Ratio 1:20 2 05 3.65 6.60 2. 05. .3. 13.35 s 120 125 34; Verysoluble. Ex. N o. 1386-----. v

Phenol for me..- Mentityi Aldehyde for resin: Furfural Date, Sept.23-24, 1948 v v [Resin made on pilot size batch, approximately 25pounds. correspondingtoSQ'a of Patent 2,499,370 but this batchdesignated as 13911.]

- Mix Which is Mix Which Re- Starting Mix fig 28 of Removed for 1 mainsas Next ac 3 Sample Starter I i Max. Max. Time u Pressu 'e, TempgrahrsSolubility Lbs. Lbs. Lbs. Lbs; Lbs. Lbs. Lbs. vLbs. l Snl- Ros- 5? 801-Res- .3% 801- Res- 5% SO]- Res- 5 vent in vent in vent in vent in FirstStage Resin to mo--- I Molal Ratio 1:1-.. }10. 25 17.75 10.25 17. 2.5 s2. 65 4. 60 0.65- 7.6 13.15 s 1. 150 M; Not soluble. Ex. N o. 1391; i

Second Stage Resin to E---" v Molal Ratiol 5-- 7 6 13.15 1.85 7.6 13.15"9. 35. 5.2 9.00 6.40 2.4 4.15. 2. 95 80 17.7 $5 Somewhat Ex No. 1405soluble.

Third Stage Resin to EtO Molal Ratio 1:10-- 4. 22 6. 98 4. 22 6. 98 10.09. 16 $4. Soluble. Ex. N o. 1415-..---

Fourth Stage Resin to Et0 Molal Ratio 1:.15 3 76 6. 24 3.76 .6. 24 .13.25 I00 1 17.1 Very soluble.

Ex. No. 142b Fifth Stage Resin to Eton.-. Molal Ratio 1:20 2 4 4.15 2.952.4 4.15 11.7 v90 is Very soluble. Ex. N0. 143!) 1 1 Phenol for resin:Para-oetyl Aldehyde for resin: Furfural Date, October 7-8, 1948 [Resinmade on pilot plant size batch, approximately 25 pounds, correspondingto 42a of Patent 2,499,370 with 206 parts by weight of commercialpara-octylphenol replacing 164 parts by weight of para-tertiaryamylphenol but this batch designated as 14411.]

- Mix Which Is Mix Which Re- Startlng Mix ig f gg of Removed for mainsas Next Sample Starter Max Pressure Temp eraig Solubility Lbs. Lbs. LbsLbs Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs ture' Sol- Rcs- Sol- Res- Sol-Res- 801- Resvent in vent in vent in vent in First Stage Resin to EtO.Molal Ratio 1:1 12 1 18.6 12.1 18.6 3.0 5.38 8.28 1.34 6.72 10.32 1.6680 150 M2 Insoluble. Ex. No. 144b-..

Second Stage Slight tend- Resln to EtO ency to- Molal Ratio 1:5.- 914.25 9.25 14.25 11.0 3.73 5.73 4.44 5.52 8. 52 6.56 100 177 A2 Ward be-Ex. No. 1455"". coming soluble.

Third Stage Resin to 1 10.... Molal Ratio 1:10- 6.72 10.32 1.66 6.7210.32 14.91 4.97 7.62 11.01 1.75 2.70 3.90 85 182 V1 Fairly solu- Ex.No. 146b-- ble.

Fourth Stage Resin to EtO. Molal Ratio 1:15- 5 52 8.52 6.56 5.52 8.5219.81 100 176 k; Readily sol- Ex. No. 1470"--- uble.

Fifth Stage Resin to Et0 Molal Ratio 1:20. 1.75 2. 3.90 1.75 2. 70 8.4160 $4 Quite solu- Ex. No. 1485"--- ble.

Phenol for resin: Para-phenyl Aldehyde for resin: Furfural Date, October11-13, 1948 [Resin made on pilot plant size batch, approximately 25pounds, corresponding to 42a of Patent 2,499,370 with 170 parts byweight of commercial paraphenylphenol replacing 164 parts by weight ofpara-tertiary amylphenol but this batch designated as 14941.]

Mix Which Is Mix Which Re- Starting Mix g gg figg of Removed for mainsas Next Sample Starter Max. Max. Time Pressure Temp erahrs Solubility lb s. gbs. Lbs l b s. abs. Lbs lbls. I bs. Lbs l'bls. r bs. Lbs

ocsoesocsoesvent in Eto vent in Eto vent in Eto vent in Eto First StageResin to EtO- Molal Ratio 1:1-. 13.9 16.7 13.9 16.7 3.0 3.50 4.25 0.8010.35 12.45 2.20 $41 Insoluble. Ex. No. l49b Second Stage Resin to Et0-Slight tend- Molal Ratio 1:5.. 10.35 12.45 2.20 10.35 12.45 12.20 5.155.10 6.06 5.20 6.26 6.14 so 183 14. Ex. No. 150b WPFd bllity.

Third Stage Resin to EtO Molal Ratio 1:10- 890 10.7 8.90 10.70 19.0 5.306.38 11.32 3.60 4.32 7.68 90 193 M2 Fairly solu- Ex. No. 1515..... ble.

Fourth Stage Resin to EtO. Molal Ratio 1:15. 5 20 6.26 6.14 5.20 6.2616.64 100 171 Readily sol- Ex. No. 152b uble.

Fifth Stage Resin to Et0 Molal Ratio 1:20. 3.60 4.32 7.68 3.60 4.3215.68 Samplesomewhat rubbery and gelat- 230 2 Ex. No. 1536-.. inous butfairly soluble

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING A HYDROPHILE ESTER IN WHICH THE ACYL RADICAL IS THAT OF ADETERGENT-FORMING MONOCARBOXY ACID HAVING AT LEAST 8 AND NOT OVER 32CARBON ATOMS, AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILEPOLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEINGOXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOTMORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OFETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE ANDMETHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANICSOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOLALYDEHYDE RESIN; SAID RESIN BEINGDERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND ANALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL;SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONALPHENOLS; SAID PHENOL BEING OF THE FORMULA